WO2009064335A1 - Séparation d'un mélange de polyols - Google Patents

Séparation d'un mélange de polyols Download PDF

Info

Publication number
WO2009064335A1
WO2009064335A1 PCT/US2008/011214 US2008011214W WO2009064335A1 WO 2009064335 A1 WO2009064335 A1 WO 2009064335A1 US 2008011214 W US2008011214 W US 2008011214W WO 2009064335 A1 WO2009064335 A1 WO 2009064335A1
Authority
WO
WIPO (PCT)
Prior art keywords
butanediol
mixture
matrix
zone
propylene glycol
Prior art date
Application number
PCT/US2008/011214
Other languages
English (en)
Inventor
Ahmad K. Hilaly
John G. Soper
Robert D. Sandage
Original Assignee
Archer-Daniels-Midland Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Archer-Daniels-Midland Company filed Critical Archer-Daniels-Midland Company
Publication of WO2009064335A1 publication Critical patent/WO2009064335A1/fr

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment

Definitions

  • the present invention relates to methods of separating mixtures of polyhydric alcohols.
  • the invention relates to methods of separating butanediol compounds, particularly 1,2- butanediol and 2,3- butanediol from a mixture of polyhydric alcohols using a chromatographic matrix.
  • the invention also relates to a simulated moving bed apparatus for use in the methods of the present invention.
  • propylene glycol and ethylene glycol are produced from petrochemical sources.
  • commercial production of propylene glycol involves the hydration of propylene oxide, which is made by the oxidation of propylene.
  • commercial production of ethylene glycol involves the hydration of ethylene oxide, made by the oxidation of ethylene.
  • propylene and ethylene are industrial by-products of gasoline manufacture; for example, they are by-products of fluid cracking of gas oils or steam cracking of hydrocarbons.
  • bio-based propylene glycol Propylene glycol that is produced by hydrogenolysis of a polyol, such as a carbohydrate, is referred to as bio-based propylene glycol.
  • glycerol Propylene glycol that is produced by hydrogenolysis of glycerol, which in turn is obtained as a by product of biodiesel production from fats and oils obtained from animal, fungal, or plant sources, is referred to as bio-based propylene glycol.
  • FRISA has established certification requirements for determining bio-based content. These methods require the measurement of variations in isotopic abundance between bio-based products and petroleum derived products, for example, by liquid scintillation counting, accelerator mass spectrometry, or high precision isotope ratio mass spectrometry. Isotopic ratios of the isotopes of carbon, such as the 13 C/ 12 C carbon isotopic ratio or the 14 C/ 12 C carbon isotopic ratio, can be determined using isotope ratio mass spectrometry with a high degree of precision. Studies have shown that isotopic fractionation due to physiological processes, such as, for example, CO 2 transport within plants during photosynthesis, leads to specific isotopic ratios in natural or bio-derived compounds.
  • Petroleum and petroleum derived products have a different 13 C/ 12 C carbon isotopic ratio due to different chemical processes and isotopic fractionation during the generation of petroleum.
  • radioactive decay of the unstable 14 C carbon radioisotope leads to different isotope ratios in bio-based products compared to petroleum products.
  • Bio-based content of a product may be verified by ASTM International Radioisotope Standard Method D 6866.
  • ASTM International Radioisotope Standard Method D 6866 determines bio-based content of a material based on the amount of bio- based carbon in the material or product as a percent of the weight (mass) of the total organic carbon in the material or product. Both bio-derived and bio-based products will have a carbon isotope ratio characteristic of a biologically derived composition.
  • Propylene glycol and ethylene glycol can be produced from petroleum or from mixtures of carbohydrates via various commercial processes, for example, a number of commercial processes that produce polyols from complex mixtures of carbohydrates exist. These processes usually produce a homologous series of glycols. Some of the resulting polyols boil so close to one another that their separation by ordinary rectification is difficult. The relative volatility is so low that a large number of theoretical plates are required to produce high purity polyols.
  • FRISA underscores the importance to the US government since 2002 of making use of biobased products, where such exist.
  • the present disclosure teaches method for meeting the need for several chemicals of biological origin by producing product streams enriched in propylene glycol, ethylene glycol, 1,2-butanediol and 1 ,3-butanediol. hi this manner, the present disclosure makes available several biobased chemicals to satisfy the need for biobased chemicals.
  • Other processes describe that, in presence of gaseous hydrogen, and metallic catalysts, glycerol can be converted to propylene glycol; 1,3 propanediol; or ethylene glycol.
  • US patents 5,276181 and 5,214,219 describe a process of hydrogenolysis of glycerol using copper and zinc catalyst in addition to sulfided ruthenium catalyst at a pressure over 2100 psi and temperature between 240- 270°C.
  • US patent 5,616,817 describes a process of preparing 1,2 propanediol by catalytic hydrogenolysis of glycerol at elevated temperature and pressure using a catalyst comprising the metals cobalt, copper, manganese and molybdenum.
  • German patent DE 541362 describes the hydrogenolysis of glycerol with a Nickel catalyst
  • US patent 4,476,331 describes a two stage method of hydrocracking carbohydrates (for example glucose), wherein a modified ruthenium catalyst is used for hydrocracking sorbitol to produce glycerol derivatives.
  • European Patent applications EP-A-0523 014 and EP-A-O 415 202 describe a process for preparing lower polyhydric alcohols by catalytic hydrocracking of aqueous sucrose solutions at elevated temperature and pressure using a catalyst whose active material comprises the metals cobalt, copper and manganese. Persoa & Tundo (hid. Eng. Chem. Res.
  • 1,2- butanediol are very small. As shown in Tables 2 and 3, the number of plates required to achieve 99% purity is very large, requiring the use of very tall distillation columns (55 plates or trays for 2,3- butanediol and 88 trays for 1,2- butanediol) and high energy inputs. The distillation columns required are so tall as to be impractical and very expensive. The present disclosure obviates the need for a distillation column, the heat energy needed to vaporize and separate the product mixture by distillation, and the vacuum pumps needed for distillation.
  • the azeotrope forming agent consists of a material selected from the group consisting of toluene, ethyl benzene, o-xylene, p-xylene, cumene, m-diisopropyl benzene, m-diethyl benzene, mesitylene, pcymene, hexane, cyclohexane, methyl cyclohexane, heptane, 3-methyl pentane, octane, decane, 2, 3,4-trimethyl pentane, dipentene, decalin, dicyclopentadiene, alpha-phellandrene, limonene, hemimellitene, myrcene, terpinolene, p-menthal, 5-diene, beta-pinene, 3-carene, I -heptene, cyclopentan
  • Azeotropic distillation using organic solvents as an agent has also proven useful for azeotropically separating ethylene glycol from 1,2- butanediol (Table 5).
  • U.S. patent 5,423,955 teaches methods to remove 1,2- butanediol from propylene glycol.
  • Surface Science 559(2-3): ⁇ 79- ⁇ S5 (2004) describe adso ⁇ tion of 2,3- butanediol on Si.
  • Khanna et al in Indian patent IN 190544 describe a process for the recovery of 2,3- butanediol from fermentation broth by treating the fermentation broth containing 2,3- butanediol with a mixture of barium hydroxide and zinc sulfate and subjecting the broth to solvent extraction using an organic solvent in a feed ratio of 3:1 at a temperature in the range of 30 to 40 0 C to obtain 2,3- butanediol.
  • the azeotropic agents used in US patents 4,935,102 and 5,432,955 can be described by Hansen solubility parameters, which are described in detail in "Hansen Solubility Parameters: A User's Handbook," by Charles M.
  • Hansen CRC Press, 1999
  • Hansen solubility parameters can be calculated using the program "Molecular Modeling Pro Plus (version 6.0.6, Norgwyn Montgomery Software, North Wales, PA) based on values published in the "Handbook of Solubility Parameters and Other Parameters” by Allen F. M. Barton (CRC Press, 1983) for solvents obtained experimentally by Hansen.
  • the Hansen "h” (hydrogen bonding) values and Hansen “p” (polarity) values at 25 °C listed in Tables 4 and 5 were calculated in this manner.
  • the use of azeotropic agents produces product streams which are contaminated with the azeotrope agent, necessitating additional separation steps and introducing cost into the process.
  • the present disclosure obviates the need for azeotropic agents, distillation columns, high temperatures and vacuum pumps yet provides streams enriched in propylene glycol and depleted of unwanted butanediol compounds.
  • the present invention provides a method of separating at least one butanediol compound from a mixture of polyhydric alcohols containing at least one butanediol compound and at least one non-butanediol compound, comprising contacting the mixture with a chromatographic matrix.
  • the butanediol compound or the non-butanediol compound, but not both, adsorbs to the chromatographic matrix.
  • the present invention further provides a method of producing a mixture of polyhydric alcohols substantially free of butanediol compounds from a mixture comprising polyhydric alcohols and at least one butanediol compound, comprising subjecting the mixture to simulated moving bed chromatography, wherein the extract comprises the mixture of polyhydric alcohols substantially free of butanediol compounds and the raffinate comprises at least one butanediol compound.
  • the present invention additionally provides a simulated moving bed apparatus comprising extract and raffinate, wherein the extract comprises propylene glycol substantially free of butanediol and the raffinate comprises at least one butanediol compound.
  • Figure 1 is a schematic example of a simulated moving bed apparatus with eight cells or columns for use in the methods of the present invention. The exit from each cell enters the top of the next cell and all the cells are linked in this manner into a loop.
  • Figures 2 and 3 are plots illustrating the results of the experiments described in
  • FIG. 8 is a plot illustrating the results of the experiments described in Example 5.
  • FIG. 11 is a diagram illustrating the simulated moving bed chromatography apparatus configured in the 1-2-2-3-4 sequence described in Example 7.
  • Figure 12 is a diagram illustrating the simulated moving bed chromatography apparatus configured in the 1-1-3-3-4 sequence described in Example 8.
  • Figure 13 is a plot illustrating the results of the experiments described in Example 6.
  • Figure 14 is a plot illustrating the results of the experiments described in Example
  • Figure 15 is a plot illustrating the results of the experiments described in Example
  • Figure 16 is a plot illustrating the results of the experiments described in Example
  • Figure 17 is a diagram illustrating the simulated moving bed chromatography apparatus configured in the 2-2-3-1-1 sequence described in Example 13.
  • bio-derived means derived from or synthesized by a renewable biological feedstock, such as, for example, an agricultural, forestry, plant, bacterial, or animal feedstock.
  • bio-based means a product that includes in whole or in significant part, biological products or renewable agricultural materials (including, but not limited to, plant, animal and marine materials) or forestry materials.
  • petroleum derived means a product derived from or synthesized from petroleum or a petrochemical feedstock.
  • butanediol compound is any alcohol derivative of the alkane, butane, which contains two hydroxyl groups.
  • Example compounds include, but are not limited to, 1,4- butanediol, l,2butanediol and 2,3- butanediol. hi some embodiments, butanediol compounds are 1,2- butanediol and 2,3- butanediol.
  • matrix also known as “chromatographic matrix” or
  • “adsorptive matrix” includes any solid substance capable of adsorbing a contaminant and includes but is not limited to carbon, charcoal (activated or non-activated), bentonite, smectite clay, montmorillonite clay, diatomaceous earth, or any other suitable adsorbent material and mixtures thereof.
  • Chromatographic matrices suitable for the methods of the present invention may be acid or base washed with or without subsequent neutralization and may comprise any physical form that accomplishes the purposes of the present invention.
  • carbon as used herein includes solid forms of carbon and includes charcoal, both activated and non-activated.
  • charcoal includes forms of carbon obtained by the partial oxidation of organic material, particularly by the burning of wood, coal, lignin, bone or other organic matter in a reducing atmosphere.
  • bentonite clay is an absorbent aluminum phyllosilicate clay that is generally impure and consists mostly of montmorillonite.
  • Montmorillonite refers to a soft phyllosilicate mineral that typically forms in microscopic crystals, forming a clay.
  • Montmorillonite is the main constituent of the volcanic ash weathering product, bentonite.
  • the water content of Montmorillonite is variable and Montmorillonite increases greatly in volume when it absorbs water. Chemically, it is hydrated sodium calcium aluminum magnesium silicate hydroxide. Potassium, iron, and other cations are common substitutes; the exact ratio of cations varies with source. Montmorillonite can be intermixed with chlorite, muscovite, illite, cookeite and kaolinite.
  • the term "adsorption” refers to a process that occurs when a gas or liquid solute accumulates on the surface of a solid or, more rarely, a liquid (adsorbent), forming a molecular or atomic film (the adsorbate). Adsorption is different from absorption, in which a substance diffuses into a liquid or solid to form a solution.
  • sorption encompasses both processes, while desorption is the reverse process. Adsorption is operative in most natural physical, biological, and chemical processes, and is widely used in industrial applications such as activated charcoal, synthetic resins and water purification.
  • Adsorption, ion exchange and chromatography are sorption processes in which certain adsorptive compounds are selectively transferred from the fluid phase to the surface of insoluble, rigid particles suspended in a vessel or packed in a column.
  • the term "adsorb” generally refers to the process where a material adsorbs to the surface of the chromatographic matrix. However, the adsorbing material may also be absorbed into the chromatographic process. In other words, the term “adsorb,” as used herein, refers to the process of adsorption, but when a material adsorbs to the chromatographic matrix, absorption may also occur, i.e., both processes may take place.
  • the process of "contacting the solvent mixture with a chromatographic matrix," as that phrase is used herein, refers to, for example, flowing a liquid solvent mixture over the solid chromatographic matrix.
  • Another example refers to allowing a liquid solvent mixture to incubate with the solid chromatographic matrix in a non-flowing condition.
  • the solvent mixture flows over the stationary chromatographic matrix wherein the matrix is divided into zones.
  • non-functional resin also known in the industry as non-ionic resin
  • non-ionic resin refers to synthetic materials, typically spherical, having a chemical structure based on a cross-linked three-dimensional polymer molecule, typically styrene and di- vinyl benzene (DVB).
  • macroporous resin refers to an inert material that is able to adsorb butanediols in preference to other polyhydric alcohols. Such resins typically have a pore diameter range of 46-700 angstroms, and the specific volume of the pores ranges from 0.5-2.1 cc/g in our results.
  • molecular sieve refers to a material containing small pores of a precise and uniform size that is used as an adsorbent for gases and liquids. In molecular sieves, molecules small enough to pass through the pores are adsorbed while larger molecules are not. Molecular sieves are different from a common filter in that they operate on a molecular level. For instance, a water molecule may be small enough to enter the molecular sieves while larger molecules are not. Because of this, they often function as a desiccant. A molecular sieve can adsorb water up to 22% of its own weight. Often molecular sieves consist of aluminosilicate minerals, clays, porous glasses, charcoals, zeolites, active carbons, or synthetic compounds that have open structures through which small molecules, such as nitrogen and water can diffuse.
  • simulated moving bed chromatography is a chromatographic technique that is based on the principle that a flow of liquid (mobile phase) moving countercurrent to a constant flow of solid (stationary phase) enhances the potential for the separation and, hence, makes the process more efficient. SMB also allows a continuous flow of feed material to be separated, which improves the throughput of the equipment compared to traditional batch chromatography and greatly simplifies handling of feed, products, and co-products. Providing a constant flow of solid is impractical in a production process. Therefore, in simulated moving bed chromatography, the solid instead is packed into columns.
  • these columns are arranged in a carousel formation made up of any number of sections or zones with one or more columns per section.
  • manifolds at the top and bottoms of the carousel provide the flow of liquid from one column to the next and allow introduction of inlets and removal of outlets.
  • two inlet streams (feed and eluent) and two outlets streams (extract (product) and rafflnate) can be directed in alternating order to and from the column ring.
  • the manifolds are rotated stepwise at regular time intervals, thus moving the inlet and outlet positions and simulating countercurrent movement of columns.
  • rafflnate refers to the effluent stream that is depleted of the desired component.
  • the rafflnate is depleted of the propylene glycol (PG) components
  • the rafflnate is the mixture of butanediol contaminants minus the remaining polyhydric alcohols.
  • the rafflnate components are the poorly adsorbed components, relative to PG.
  • the rafflnate components are the more strongly bound material, relative to PG.
  • rafflnate is contained in one of the outlet streams of the SMB apparatus, hi some embodiments of the present invention, the rafflnate is a mixture of some polyhydric alcohols plus the butanediol contaminants, hi some embodiments, the butanediol contaminants adsorb to the chromatographic matrix.
  • extract also referred to as "product,” as used herein, refers to the effluent stream that contains the polyhydric alcohols, hi some embodiments, the extract is depleted of all components except the propylene glycol (PG) components. Typically, but not always, the extract are the unadsorbed or intermediately adsorbed components. Typically, one of the outlet streams in simulated moving bed chromatography contains extract or product.
  • PG propylene glycol
  • the term "substantially free of butanediol compounds” refers to mixture of polyhydric alcohols or a propylene glycol product that contains less than about 2% butanediols.
  • the term also can refer to a mixture of polyhydric alcohols that is classified as a U.S.D.A. Certified Bio-based Product according to the Farm Security and Rural Investment Act of 2002, section 9002 (7 U.S.C. 8102).
  • the term “elution” refers to the process of extracting one material from another by washing with a solvent to remove adsorbed material from an adsorbent.
  • feed mixture is a mixture containing one or more extract components and one or more raffinate components to be separated by the methods of the present invention.
  • feed stream indicates a stream of a feed mixture which is passed into contact with the adsorbent used in the methods of the present invention.
  • ternary separation refers to a separation of a mixture comprising at least three compounds into three streams, each of which is enriched in a different compound which can be recovered from the feed mixture. This is also called “ternary desorption".
  • three effluent streams may be employed, hi some embodiments, one effluent stream is enriched in PG, a second effluent stream may be enriched in another component of the feed mixture, such as 2,3-butanediol.
  • a third effluent stream may be enriched in another component of the feed mixture, such as 1,2- butanediol.
  • system refers to an apparatus comprising an SMB apparatus, together with a matrix and conduits bringing feed mixture to the apparatus and conduits bringing extracts or products from the apparatus comprise a separation system.
  • the system may be used to produce an extract or product mixture of polyhydric alcohols substantially free of butanediol compounds from a mixture comprising polyhydric alcohols and at least one butanediol compound, comprising contacting the mixture with a matrix in a simulated moving bed chromatography apparatus, wherein an extract or product stream is enriched in propylene glycol and depleted of butanediol compounds and a raffinate is depleted of propylene glycol and enriched in butanediol compounds relative to a feed stream.
  • the invention pertains to the removal of butanediols, such as 1 ,2- butanediol
  • 1,2- BDO 2,3- butanediol
  • 2,3- BDO 2,3- butanediol
  • the mixture of polyhydric alcohols contains not only BDOs, ethylene glycol, propylene glycol and glycerol, but also lactic acid (2-hydroxypropanoic acid) and other organic acids, hi some embodiments, the invention results in a propylene glycol product that is substantially free of all contaminants.
  • the mixture of polyhydric alcohols results from the hydro cracking of carbohydrates or hydrogenolysis of alcohols.
  • the boiling points of the polyhydric alcohols contained in the mixture are quite similar to one another, resulting in difficulties in isolating the desired product, such as propylene glycol or ethylene glycol, in a substantially purified form.
  • Some prior methods have used azeotropic solvent mixtures for separating substantially purified propylene glycol and ethylene glycol from 1,2- butanediol and 2,3- butanediol.
  • Suitable azeotrope forming agents are typically organic compounds and are difficult to process and handle due to environmental regulations. Azeotrope forming agents can also be expensive.
  • This present invention avoids the use of expensive solvents, complicated azeotropes, and complicated distillation techniques and thus presents a unique and convenient way to remove butanediol impurities from propylene glycol and ethylene glycol by using an adsorption or chromatographic technique.
  • the invention also provides methods to obtain a propylene glycol product that is substantially free of other contaminants, i.e., contains less than 2% BDOs, ethylene glycol, glycerol and lactic acid (or other organic acids).
  • the present invention provides the use of adsorbents for removing 1,2- butanediol and 2,3- butanediol from a mixture of polyhydric alcohols.
  • adsorbents for removing 1,2- butanediol and 2,3- butanediol from a mixture of polyhydric alcohols.
  • a mixture of propylene glycol, ethylene glycol, glycerol, low levels of butanediols, lactic acid, sodium hydroxide and other organic acids are produced from hydrogenolysis.
  • the adsorption techniques of the present invention allow even these low levels of butanediols to be separated from other polyhydric alcohols.
  • the present invention provides methods of separating at least one butanediol compound from a mixture of polyhydric alcohols containing at least one butanediol compound and at least one non-butanediol compound, hi some embodiments, such methods comprise contacting the mixture with a chromatographic or adsorptive matrix, wherein at least one butanediol compound or at least one non-butanediol compound preferentially adsorbs to the chromatographic matrix, compared to the other components of the mixture.
  • the methods of the present invention include methods where the butanediol compounds preferentially adsorb to the chromatographic, or adsorptive matrix, or the polyhydric alcohols such as propylene glycol or ethylene glycol preferentially adsorb to the chromatographic matrix.
  • the butanediol compounds that adsorb to the matrix can be eluted and recovered.
  • the chromatographic matrix preferentially adsorbs polyhydric alcohols other than butanediol compounds
  • the polyhydric alcohols that adsorb to the matrix can be eluted and recovered.
  • the material that preferentially adsorbs to the matrix elutes from the matrix without the need for an additional eluent.
  • a mixture of propylene glycol, ethylene glycol, glycerol, BDOs, and organic acids are contacted with the chromatographic matrix. The least adsorbed component elutes from the matrix first and the most adsorbed component elutes from the component last, with the intermediately adsorbed components eluting in between the first and the last components.
  • the butanediol component for example, adsorbs to the chromatographic matrix and elutes from the matrix upon feeding an eluent, such as a primary alcohol, into the SMB apparatus.
  • an eluent such as a primary alcohol
  • one of the polyhydric alcohol components such as propylene glycol, adsorbs to the matrix and is eluted from the matrix.
  • the product comprises a stream that is enriched in propylene glycol and is and depleted of other polyhydric alcohols, hi this embodiment, the propylene glycol component is poorly adsorbed to the matrix.
  • Two raffinate discharges are therefore released from the SMB apparatus, one enriched in polyhydric alcohols and one enriched in BDO components.
  • the raffinate discharge enriched in polyhydric alcohols is eluted from the SMB apparatus with deionized water and the raffinate discharge stream that is enriched in BDO components is eluted using methanol.
  • At least one butanediol compound adsorbs to the chromatographic matrix and the mixture of polyhydric alcohols comprises propylene glycol, ethylene glycol or a mixture thereof, hi some embodiments, at least one butanediol compound is 1,2- butanediol, 2,3- butanediol, or a mixture thereof.
  • Suitable chromatographic matrices for butanediol adsorption include those that adsorb butanediol compounds by covalent, ionic, hydrogen or any other polarity based binding.
  • the chromatographic, or adsorptive, matrix comprises a material that selectively adsorbs at least one butanediol compound over the remaining components of the mixture of polyhydric alcohols.
  • matrices include, but are not limited to, carbon black, carbon powder, activated charcoal, non-activated charcoal, diatomaceous earth, silica, alumina, clay, and resin.
  • the chromatographic matrix is a carbon powder.
  • the chromatographic, or adsorptive, matrix is alumina.
  • the alumina is neutral alumina, basic alumina and acidic alumina.
  • the present invention also provides chromatographic matrices comprising clay.
  • clays suitable for use in the present invention include, but are not limited to, bentonite clay, smectite clay and montmorillonite clay.
  • the chromatographic matrix is a resin material, such as an ion exchange resin.
  • the ion exchange resin is selected from the group consisting of a weak acid cation exchange resin, a strong acid cation exchange resin, a weak base anion exchange resin and a strong base anion exchange resin, hi further embodiments, the resin is a carbon-based macroporous resin.
  • Such carbon-based macroporous resin includes, but is not limited to Lewatit AF-5.
  • the chromatographic matrix is a non-ionic resin. Non-ionic resins are also referred to as non-functional resins.
  • Such resins can be, but are not limited to, Lewatit S7768, Lewatit VP OC 1064, Mitsubishi SP70, Mitsubishi SP700, Mitsubishi HP21, Mitsubishi SP207, Mitsubishi SP825, Mitsubishi SP825L, Mitsubishi SP850, Dow V493, Dow SD-2, Finex FAD70, Finex FADl 18, Purolite MN200, Rohm & Haas XAD4, and Rohm & Haas XPF66.
  • the chromatographic, or adsorptive, matrix is a molecular sieve.
  • Suitable molecular sieves include, but are not limited to, UOP Molecular Sieve from UOP (UOP LLC, Des Plaines, IL USA) Molecular Sieve Type 3A; (Chemical Name: Sodium/Potassium Aluminosilicate; Synonyms: Zeolite); 564ET3A and 562Et from Grace Davison (W.R. Grace & Co.-Conn., Baltimore, MD USA) Sylobead 562Et: Sylobead 564Et: crystalline aluminosilicate; type Z Grade 3A-8 from Sphinx (Sphinx Adsorbents, Inc.
  • Chromatographic, or adsorptive, matrices can be in any suitable physical form.
  • Suitable examples include, but are not limited to, powder, pellets, granules or a combination thereof.
  • activated granular carbon or bentonite having 12x40, 20x40, 30x60, 8x30 or any similar sieve size may be used.
  • Chromatographic matrices suitable for the methods of the invention may be acid or base washed with or without subsequent neutralization. It is well known in the art that adsorptive matrices may be reused through regeneration, for example, by acidification, alkalization or change in polarity of solvent using for regeneration. As such, matrices such as carbon, for example, may be regenerated for multiple uses. Although such regenerated matrices may lose adsorptive capacity with use, such additional steps of regeneration are encompassed by the present invention.
  • the present invention further provides a method of producing a mixture of polyhydric alcohols substantially free of butanediol compounds from a mixture comprising polyhydric alcohols and at least one butanediol compound.
  • the mixture of polyhydric alcohols results from the catalytic hydrogenolysis of glycerol.
  • Catalytic hydrogenolysis also referred to as hydrocracking, is a process whereby a polyol, such as a sugar, glycerol or glycols are reacted with hydrogen to produce other polyols.
  • the polyols produced from this process often comprise a mixture of polyols having a lower average molecular weight than the starting material.
  • the mixture of polyols produced from catalytic hydrogenolysis provide a suitable material for the methods of the present invention.
  • the mixture of polyhydric alcohols results from the catalytic hydrogenolysis of glycerol.
  • the glycerol in turn, is a byproduct from the production of biodiesel via a transesterification reaction between an oil, such as a vegetable oil, and an alcohol.
  • the catalytic hydrogenolysis of polyols produces not only desired components, such as propylene glycol and ethylene glycol, but also can produce several unwanted products, such as 1,2- butanediol, 1,3- butanediol, 1,4- butanediol and 2,3- butanediol.
  • the reaction product of the catalytic hydrogenolysis of a polyol such as glycerol, produces a mixture of polyhydric alcohols that contain from about 0.1% to about 13% by volume butanediol contaminants.
  • the mixture of polyhydric alcohols is subjected to simulated moving bed chromatography, wherein the extract, or product comprises the mixture of polyhydric alcohols substantially free of butanediol compounds and the raffinate comprises at least one butanediol compound.
  • the raffinate i.e., the component of the mixture that does not preferentially adsorb to the chromatographic matrix, is the mixture of polyhydric alcohols substantially free of the butanediol contaminants discussed above.
  • the extract by contrast, is the component of the mixture that preferentially adsorbs to the chromatographic matrix.
  • the raffinate is substantially free of butanediol compounds, meaning that the raffinate contains less than about 2% butanediol compounds.
  • the term "substantially free of butanediol components" also can refer to a mixture of polyhydric alcohols that is classified as a U.S.D.A. Certified Bio-based Product according to the Farm Security and Rural Investment Act of 2002, section 9002 (7 U.S.C. 8102).
  • the present invention additionally provides a method of operating a simulated moving bed apparatus so that a ternary separation is achieved.
  • a ternary separation can be achieved.
  • a feed mixture comprising PG and one or more butanediol, such as 1,2-BDO and 2,3-BDO, can be separated into an effluent enriched in PG, an effluent enriched in 1,2-BDO, and an effluent enriched in 2,3-BDO.
  • SMB adsorptive separation units simulate countercurrent movement of the adsorbent and the feed stream using established commercial technology.
  • the adsorbent is loaded into several columns (cylindrical adsorbent chambers), often arranged in a ring and mounted in a carousel for convenience. Each column is connected to the two adjacent columns to allow the flow of liquids between columns.
  • manifolds are positioned at the top and bottoms of the columns, and by shifting the manifolds stepwise with respect to the beds, the movement of the bed is simulated.
  • the SMB unit has at least four streams (feed, eluent, extract and raffinate) employed in this procedure and the location at which the feed and desorbent streams enter the chamber and the extract and raffinate streams leave the chamber are simultaneously shifted in the same direction at set intervals.
  • feed, eluent, extract and raffinate employed in this procedure and the location at which the feed and desorbent streams enter the chamber and the extract and raffinate streams leave the chamber are simultaneously shifted in the same direction at set intervals.
  • Each shift in the location of these transfer points delivers or removes liquid from a different sub-bed of adsorbent within the chamber.
  • These processes typically include at least three or four separate steps which are performed sequentially in separate zones within a mass of adsorbent or matrix retained in one or more vertical cylindrical adsorption chambers (columns).
  • Each of these zones normally is formed from a plurality of beds of adsorbent, sometimes referred to as sub- beds, with the number of beds per zone ranging from 1 or 2 up to 8-12. All of the beds are contained in one or more vertical vessels referred to herein collectively as the adsorbent chamber.
  • the beds are structurally separated from one another by a horizontal liquid collection/distribution grid. Each grid is connected to a transfer line defining a transfer point at which process streams such as the raffinate and extract stream enter and leave the vertical adsorption chambers.
  • a feed mixture containing a mixture of compounds is contacted with the adsorbent at adsorption conditions and one compound(s) or class of compounds is selectively adsorbed and retained by the adsorbent while the other compounds of the feed mixture are relatively unabsorbed.
  • the adsorbent contains a near equilibrium loading of the more selectively adsorbed compound, it is referred to as a "rich" adsorbent.
  • the unabsorbed (raffinate) components of the feed mixture are then removed from the interstitial void spaces between the particles of adsorbent and from the surface of the adsorbent.
  • This depleted liquid and any eluent which becomes admixed with it during passage through the adsorption zone in this step is removed from the process as a process stream referred to as the raffinate stream.
  • the adsorbed compound is then recovered from the rich adsorbent by contacting the rich adsorbent with a stream comprising the eluent at desorption conditions in a desorption step.
  • the eluent displaces a stream that is enriched in the desired compound to form an extract stream, which, in some embodiments, is transferred to a separation means for recovery of the desired compound from the extract stream containing a mixture of the desired compound and eluent.
  • all or a part of the extract stream or all or a part of the raffinate stream, or both are passed to separation means, typically fractional distillation columns, to recover at least a portion of the eluent and a portion of the extract or the raffinate, or both.
  • separation means typically fractional distillation columns
  • What is produced from the separation means is therefore an extract product, where the extract component is present in a higher concentration in the extract product than found in the extract stream.
  • the raffinate product produced after the separation process contains a higher percentage of raffinate components than found in the raffinate stream.
  • adsorbed butanediols are recovered from the adsorbent using an eluting solvent such as a primary alcohol that will allow recovery of substantially pure butanediols after distillation of the primary alcohol.
  • an eluting solvent such as a primary alcohol that will allow recovery of substantially pure butanediols after distillation of the primary alcohol.
  • the material containing butanediols is transported or shipped (i.e., distributed) to another location for subsequent incorporation into a composition.
  • the container or the composition may also be associated with indicia indicating that the material contains less than a specified amount of the butanediols.
  • Suitable eluting solvents also referred to as eluents, for use in the present invention include, but are not limited to water, such as deionized water, and primary alcohols, such as methanol and ethanol. Additional suitable eluents can be used and techniques to determine such eluents are known to those of skill in the art.
  • the mixture of polyhydric alcohols is contacted with a chromatographic matrix.
  • Contacting the mixture of polyhydric alcohols with the chromatographic matrix comprises flowing the mixture of polyhydric alcohols over or through the chromatographic matrix.
  • the product, or extract comprises a mixture of polyhydric alcohols, which include propylene glycol.
  • the raff ⁇ nate comprises butanediol compounds.
  • the product comprising the mixture of polyhydric alcohols is then subjected to further separation steps to recover substantially purified propylene glycol.
  • the present invention also provides a simulated moving bed apparatus comprising raffinate and extract, wherein the product comprises propylene glycol substantially free of butanediol and the raffinate comprises at least one butanediol compound, hi another embodiment, the present invention also provides a simulated moving bed apparatus comprising raffinate, product PG, and recycled raffinate wherein the product comprises propylene glycol substantially free of butanediol, the raffinate comprises 2,3-butanediol, and the recycled raffinate comprises 1,2-butanediol.
  • the present invention also provides a simulated moving bed apparatus comprising raffinate 1, raffinate 2, and product PG wherein the product PG comprises propylene glycol substantially free of butanediol, the raffinate 1 comprises butanediols, and the raffinate 2 comprises 1,2-butanediol.
  • FIG 1 is a simplified schematic of an SMB apparatus.
  • the exit from each cell enters the top of the next cell.
  • Figures 11 and 12 illustrate examples of a simulated moving bed apparatus for use in the methods of the present invention.
  • the SMB apparatus is drawn schematically using a set of cells or columns. The exit from each cell enters the top of the next cell and all the cells are linked in this manner into a loop.
  • a typical SMB apparatus contains four valves: a feed valve, an eluent valve, an extract valve and a raffinate valve.
  • the SMB apparatus contains an additional valve to remove the third stream.
  • the third stream may be an additional extract stream or may be an additional raffinate stream.
  • the valves are switched periodically, such that, for example, the feed valve is switched in the same direction as the liquid flow.
  • the other three (or four) valves, eluent, extract and raffinate, must also move in this manner.
  • the SMB apparatus also optionally comprise a temperature-control device that keeps the temperature of the apparatus from about 30 0 C to 70 °C.
  • SMB apparatus is from about 3 to 98 gallons per minute ("GPM"), in some embodiments from about 20- 40 GPM, and in other embodiments, about 30 GPM.
  • GPM gallons per minute
  • the zone bracketed by extract or product discharge port and the feed inlet port is from about 29 GPM to about 313 GPM, in some embodiments from about 50 to 70 GPM, and in further embodiments, about 60 GPM.
  • the eluent flow is from about 38
  • GPM to 546 GPM in some embodiments from about 55 GPM to about 85 GPM, and in further embodiments, about 75 GPM.
  • the rinse flow e.g., methanol flow
  • the rinse flow e.g., methanol flow
  • the rinse flow is from about 28 GPM to about 313 GPM, in some embodiments from about 90 GPM to about 100 GPM, and in further embodiments, about 97 GPM.
  • a preliminary test may be employed to test adsorbents and determine optimal conditions for simulated moving bed chromatography.
  • a pulse test a particular feed mixture and desorbent material are examined to measure adsorbent characteristics such as adsorptive capacity, selectivity, resolution and exchange rate.
  • the basic pulse test apparatus consists of a tubular adsorbent chamber (e.g. a glass column) containing adsorbent and having an inlet and outlet at opposite ends of the chamber. The column is jacketed for temperature control.
  • Quantitative and qualitative analytical equipment such as refractometers, polarimeters and chromatographs can be attached to an outlet line of the chamber and used to detect quantitatively and/or determine qualitatively one or more components in the effluent stream leaving the adsorbent chamber.
  • the adsorbent is first filled to equilibrium with a particular eluent by passing the eluent through the adsorbent chamber.
  • a pulse of the feed mixture sometimes diluted in desorbent, is then injected or applied to the top of the adsorbent bed. Eluent flow is resumed, and the feed components are eluted as in a liquid-solid chromatographic operation.
  • the effluent can be analyzed on-stream. Alternatively, or in addition effluent fractions can be collected and later analyzed separately. Traces of the envelopes of corresponding component peaks can then be plotted in terms of component concentration versus quantity of effluent.
  • the adsorbent/eluent performance can normally be rated in terms of retention volume for an extract or a raffinate component, selectivity for one component with respect to the other, stage time, the resolution between the components and the rate of desorption of an extract component by the eluent.
  • the retention volume of an extract or a raffinate component may be determined from the distance between the center of the peak envelope of an extract or a raffinate component and the peak envelope of a tracer component or some other known reference point. It is expressed in terms of the volume in cubic centimeters of eluent pumped during the time interval corresponding to the distance between the peak envelopes.
  • PG reactor product was prepared by hydrogenolysis of a 40% solution of glycerol containing sodium hydroxide in a 2000ml high-pressure Stainless Steel 316 reactor as described in US patent application 60/913,572, filed April 24, 2007. Solid catalyst was loaded in the reactor to a final volume of 1000 ml of catalyst. The reactor was jacketed with a hot oil bath to provide for the elevated temperature for reactions and the feed and hydrogen lines were also preheated to the reactor temperature. A solution of a 40% solution of glycerol containing sodium hydroxide was fed through the catalyst bed at LHSV ranging from 0.5hr-l to 2.5hr-l.
  • Hydrogen was supplied at 1200-1600 psi and was also re-circulated through the reactor at a hydrogen to glycerol feed molar ratio of from 1.4:1 to 1.6:1. Between 47.7-96.4% of the glycerol was converted to polyhydric alcohols and between 36.3-55.4% of propylene glycol was produced. In addition to propylene glycol, the hydrogenolysis reaction produced 0.04-2.31% unwanted BDO, which present a problem for recovery of pure propylene glycol.
  • the horizontal axis is the bed volume (“BV")
  • the left vertical axis is the concentration in percentage of propylene glycol, i.e., 1, 2-propanediol, and ethylene glycol in the column effluent.
  • the right vertical axis is shows butanediol concentration in the column effluent. Effluent fractions enriched in PG and EG and depleted of BDO were recovered, and BDO was recovered from the carbon bed by elution with 100% ethanol (Figure 3).
  • Figure 3 shows the results of this desorption (elution, or stripping) or regeneration test.
  • the horizontal axis is the BV
  • the vertical axis is the concentration, in percentage, of the propylene glycol and ethylene glycol which remained in the column bed using ethanol regeneration.
  • Figures 4 and 5 graphically illustrate the results of this experiment.
  • Figure 4 is a breakthrough (capacity) plot showing the unadsorbed components relative to volumes of feed fed through the column, leading to breakthrough capacity.
  • the horizontal axis is the bed volume (“BV")
  • the left vertical axis is the concentration in percentage of propylene glycol and ethylene glycol in the column effluent.
  • FIG. 5 is a plot of a desorption (stripping) or regeneration test using 100% ethanol.
  • the horizontal axis is the BV
  • the vertical axis is the concentration, in percentage, of the propylene glycol and ethylene glycol which remained in the column bed using ethanol regeneration.
  • a feed enriched in 2,3- butanediol in PG reactor product was prepared by mixing 1 mL pure 2,3- butanediol (Spectrum Chemical Co., Gardena, CA) into every 10 mL reactor product.
  • the composition of the PG reactor product control feed ("not spiked") and enriched feed (spiked) with BDO follows in the table below.
  • PG propylene glycol
  • EG ethylene glycol
  • DEG diethylene glycol
  • Na sodium ion.
  • a system for conducting simulated moving bed chromatography is prepared in a sequence of zones comprising 12 columns filled with Dowex V-493, a non-functional polymeric adsorbent resin, as the matrix, in a carousel in a simulated moving bed (SMB) apparatus ( Figure 11).
  • Zone I is an adsorption zone
  • zone II is an enrichment zone
  • zone HI is a desorption zone
  • zone IV is a solid regeneration zone
  • zone V is a regeneration rinse zone ( Figure 11).
  • the SMB apparatus contains 12 columns on a carousel arranged in zones comprising the following number of columns in zones I- V, respectively: 4-3-2-2- 1.
  • the SMB apparatus contains provisions for rotating the columns in the direction opposite the flow of fluid at defined intervals, called the "Step Time”.
  • the step time is 10 minutes.
  • the SMB apparatus, together with the matrix and conduits bringing feed to the apparatus and conduits bringing products from the apparatus comprise a separation system.
  • Zone I the Adsorption zone is defined (bracketed) by the reactor product feed
  • PG reactor product is applied continuously to the adsorption zone at 4 ml/min, joining the flow from the enrichment section from zone II in the SMB.
  • Adsorption of several intermediately bound components (PG, and ethylene glycol (EG)), and highly bound components (2,3- BDO) takes place in the adsorption zone and a raffinate stream enriched in unbound and more lightly bound components, sodium hydroxide (NaOH), 1,2- BDO, and glycerol is continuously passed out of the SMB unit at the end of zone I as "Recycled Raffinate".
  • This material containing glycerol and NaOH (with some 1 ,2- BDO and EG) can be recycled back to the PG reactor for conversion to PG.
  • Zone II is the zone defined (bracketed) by the product PG discharge port and the reactor product feed inlet port. There are 3 columns in this zone (columns 6-8 in Figure 11). The flow in this zone is 33.9 ml/minute. The primary purpose of this zone is to increase the amount of PG bound to the matrix and allow it to displace the lightly bound components sodium hydroxide (NaOH), 1,2 -BDO, and glycerol. This increases the PG product purity.
  • NaOH sodium hydroxide
  • 1,2 -BDO 1,2 -BDO
  • glycerol glycerol
  • Zone III (the Desorption zone) is the zone bracketed by the Deionized (DI) elution water inlet port and the product PG discharge port. There are 2 columns in this zone (columns 4 & 5 in Figure 11). The primary purpose of this zone is to desorb (strip) the PG product from the matrix. The DI elution water is pumped into this zone through the DI elution water inlet at 36.0 ml/minute, causing the PG to desorb from the matrix.
  • DI Deionized
  • an effluent enriched in PG and depleted of NaOH, glycerol, EG and 1,2-BDO is continuously eluted from the SMB and allowed to pass out of the SMB through the product PG discharge port as an effluent labeled "Product PG".
  • Zone FV (the Regeneration zone) is the zone bracketed by the methanol inlet port and the raffinate (2,3 -BDO) discharge port. There are 2 columns in this zone (columns 2 & 3 in Figure 11). The primary purpose of this zone is to desorb (strip) the tightly bound components (2,3-BDO) and other potential fouling compounds from the matrix. The flow in this zone is 36.0 ml/minute. 2,3-BDO is allowed to pass out of the SMB through the raffinate discharge port as an effluent labeled "Raffinate (2,3-BDO)".
  • Zone V (the Regeneration Rinse zone) is the zone bracketed by the DI water inlet port and the methanol inlet port. There is 1 column in this zone (column 1 in Figure 11). The primary purpose of this zone is to remove the methanol as mobile phase and prepare the matrix for the Adsorption zone (zone I). The flow into this zone is 15.0 ml/minute, which is sufficient to displace the void fraction methanol from the column.
  • the simulated moving bed chromatography is configured in a 1-1-3-3-4 sequence in a simulated moving bed (SMB) apparatus.
  • the matrix used is Mitsubishi SP700, nonfunctional polymeric adsorbent resin.
  • Zone I is an adsorption zone; zone ⁇ is an enrichment zone; zone El is a desorption zone; zone IV is a solid regeneration zone; and zone V is a regeneration rinse zone ( Figure 12).
  • the SMB apparatus contains 12 columns on a carousel, and provisions for rotating the columns in the direction opposite the flow of fluid at defined intervals, called the "Step Time". The step time is 10 minutes.
  • Zone I (the Adsorption zone) is defined by the feed, propylene glycol (PG) inlet and the Product PG discharge ports.
  • PG reactor product enriched with BDO or control is applied continuously in the adsorption zone at 9.6 ml/min, joining the flow in the SMB.
  • the components of the feed material chromatographically move through the columns in the zone such that PG, ethylene glycol (EG), and lightly bound and unbound components such as sodium hydroxide (NaOH), 1 ,2- BDO, and glycerol are continuously passed out of the SMB unit at the end of zone I as "PG Product" and the 2,3- BDO component is retained with the solid phase.
  • Zone II (the Depletion zone) is the zone defined by the Raffinate 1 discharge and the feed inlet ports (columns 6-8 in Figure 12). The flow in this zone is 38.4 ml/minute. There are 3 columns in this zone. The primary purpose of this zone is to deplete the matrix loading of PG and enrich it with the butanediol components.
  • Zone III (the Desorption zone) is the zone defined by the Deionized (DI) water elution inlet and the Raffinate 1 discharge ports (columns 3, 4 & 5 in Figure 12). There are 3 columns in this zone. The primary purpose of this zone is to strip the butanediol components from the resin matrix. The DI water elution is pumped into this zone through the DI water inlet at 48.0 ml/minute, and it strips BDO from the matrix.
  • DI Deionized
  • an effluent enriched in BDO and depleted of PG, EG, and glycerol is continuously eluted from the SMB and allowed to pass out of the SMB as an effluent labeled "Raffinate 1".
  • Zone IV (the Regeneration zone) is the zone defined by the Raffinate 1 (BDO) discharge and methanol inlet ports (column 2 in Figure 12). There is 1 column in this zone. The primary purpose of this zone is to strip the tightly bound components (1,2- BDO and 2,3- BDO) from the matrix and to remove other potential fouling compounds that were adsorbed. The flow in this zone is 30.0 ml/minute.
  • Zone V (the Regeneration rinse zone) is the zone defined by the DI water inlet and methanol inlet ports (column 1 in Figure 12). There is 1 column in this zone. The primary purpose of this zone is to remove the methanol as mobile phase and prepare the matrix for the adsorption zone (zone I). The flow in this zone is 19.2 ml/minute, which is just about enough to displace the void fraction methanol from the column.
  • Example 9
  • 3-butanediol was contacted with 100ml Sepabeads SP70 resin matrix (Mitsubishi) substantially as in Example 2. Column temperature was set at 45 degrees C. The feed was eluted with deionized water at a flow rate of 3 mL/min for approximately 2 bed volumes (200 mL). At approximately 2 bed volumes, the deionized water eluent was replaced with 99% methanol eluent. The results are shown in Figure 13.
  • Ternary separation could be effected by setting up the Simulated Moving Bed device to collect the fraction eluting at 0.4 to 1.4 BV to obtain an effluent enriched in sodium, glycerol ethylene glycol, and propylene glycol; a second fraction eluting at 1.4 to 2.2 bed volumes to obtain an effluent enriched in 2,3- BDO; and a third fraction eluting at 2.2 to 3.2 BV to obtain a fraction enriched in 1,2- BDO.
  • 3-butanediol was contacted with 100ml Sepabeads SP700 resin (Mitsubishi) substantially as in Example 2. Column temperature was set at 45 degrees C. The feed was eluted with deionized water at a flow rate of 3 mL/min for approximately 2 bed volumes (200 mL). At approximately 2 bed volumes, the deionized water eluent was replaced with 99% methanol eluent. The results are shown in Figure 14.
  • the portion of the figure from 0 to 2.0 bed volumes depicts separation in a chromatographic mode, in which separation is based on the differences in affinity between the chromatographic bed and the components in the mixture, which causes retardation of certain substances relative to others in a given eluent (deionized water).
  • these components will be separated and elute in Zones I- HI (columns 4-12) through two separate outlet ports.
  • a first outlet port will remove the fraction in bed volumes 0 to 0.9, to provide an effluent enriched in sodium and 1,2- BDO.
  • a second outlet port will remove the fraction from 0.9 to 2.0 bed volumes to provide an effluent enriched in ethylene glycol and propylene glycol.
  • the portion of the figure from 0 to 2.0 bed volumes depicts separation in a chromatographic mode, in which separation is based on the differences in affinity between the chromatographic bed and the components in the mixture, which causes retardation of certain substances relative to others in a given eluent (deionized water), hi an SMB apparatus as depicted in Figure 11, these components will be separated and eluted in Zones I- III (columns 4-12).
  • the portion of the figure from 2.0 to 3.2 bed volumes depicts separation in an adsorb/desorb mode.
  • the simulated moving bed chromatography was configured in a 2-2-3-1-1 sequence in a simulated moving bed (SMB) apparatus ( Figure 17) and filled with Dowex V-493, a non- functional polymeric adsorbent resin, as the matrix.
  • the matrix was arranged in zones. Zone I was an adsorption zone; zone II was an enrichment zone; zone HI was a desorption zone; zone IV was a solid regeneration zone; and zone V was a regeneration rinse zone ( Figure 17).
  • the SMB apparatus contained 9 columns on a carousel, and provisions for rotating the columns in the direction opposite the flow of fluid at defined intervals, called the "Step Time". The step time was 10 minutes.
  • Zone I the Adsorption zone was defined (bracketed) by the reactor product feed
  • Zone II (the Enrichment zone) was the zone defined (bracketed) by the product
  • Zone III (the Desorption zone) was the zone bracketed by the Deionized (DI) elution water inlet port and the product PG discharge port. There were 3 columns in this zone (columns 4-7 in Figure 17). The primary purpose of this zone was to desorb (strip) the PG product from the matrix. The DI elution water was pumped into this zone through the DI elution water inlet at 4.4 ml/minute, causing the PG to desorb from the matrix.
  • DI Deionized
  • Zone IV (the Regeneration zone) was the zone bracketed by the methanol inlet port and the raffinate (BDO) discharge port. There were 2 columns in this zone (columns 3 & 4 in Figure 17). The primary purpose of this zone was to desorb (strip) the tightly bound components (BDO) and other potential fouling compounds from the matrix. The flow of methanol into this zone was 6 ml/minute. BDO was allowed to pass out of the SMB through the raffinate discharge port as an effluent labeled "Raffinate BDO".
  • Zone V (the Regeneration Rinse zone) was the zone bracketed by the DI water inlet port and the methanol inlet port. There were 2 columns in this zone (columns 1 & 2 in Figure 17). The primary purpose of this zone was to remove the methanol as mobile phase and prepare the matrix for the Adsorption zone (zone I). The flow of DI water into this zone was 4.4 ml/minute, which was sufficient to displace the void fraction methanol from the column.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention porte sur des procédés de séparation d'au moins un composé butanediol à partir d'un mélange contenant des polyols et des composés butanediols. Le mélange de polyols contient typiquement du propylèneglycol et de l'éthylèneglycol en plus des contaminants butanediols. Les contaminants butanediols sont retirés par mise en contact du mélange avec une matrice chromatographique. Soit les composés butanediols soit les composés non-butanediols s'adsorbent sur la matrice chromatographique. Si on le désire, les composés adsorbés peuvent être élués de la matrice, purifiés et utilisés dans des produits.
PCT/US2008/011214 2007-11-09 2008-09-26 Séparation d'un mélange de polyols WO2009064335A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US98682707P 2007-11-09 2007-11-09
US60/986,827 2007-11-09
US12/235,192 US8177980B2 (en) 2007-11-09 2008-09-22 Separation of a mixture of polyhydric alcohols
US12/235,192 2008-09-22

Publications (1)

Publication Number Publication Date
WO2009064335A1 true WO2009064335A1 (fr) 2009-05-22

Family

ID=40622717

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2008/011214 WO2009064335A1 (fr) 2007-11-09 2008-09-26 Séparation d'un mélange de polyols

Country Status (2)

Country Link
US (1) US8177980B2 (fr)
WO (1) WO2009064335A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105985220A (zh) * 2014-11-26 2016-10-05 义守大学 醇类化合物的纯化方法

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102372598A (zh) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 乙二醇和丁二醇的分离方法
CN102372599B (zh) * 2010-08-23 2013-12-04 中国石油化工股份有限公司 分离乙二醇和丁二醇的方法
WO2012125276A2 (fr) 2011-03-14 2012-09-20 Archer Daniels Midland Company Procédés perfectionnés de production de propylène glycol biodérivé
US10017439B2 (en) * 2014-04-10 2018-07-10 Archer Daniels Midland Company Process for the isolation of reaction products from sugar alcohol or anhydrosugar alcohol hydrogenolysis reaction mixtures using simulated moving bed chromatography
AU2014390000B2 (en) * 2014-04-10 2018-08-16 Archer Daniels Midland Company Dehydration of a sugar alcohol with mixed combination of acid catalysts
CN106232562B (zh) 2014-04-22 2019-01-15 阿彻丹尼尔斯米德兰德公司 制造生物衍生的丙二醇的改进的方法
EP3160928B1 (fr) 2014-06-30 2023-10-25 Topsoe A/S Procédé pour la préparation d'éthylène glycol à partir de sucres
BR112016030824B1 (pt) 2014-06-30 2021-02-23 Haldor Topsoe A/S processo para a preparação de etileno glicol a partir de açúcares
US11040903B2 (en) * 2015-10-05 2021-06-22 The Chemours Company Fc, Llc Purification of NaCl brine containing iodine
CN108367212A (zh) * 2015-12-01 2018-08-03 陶氏环球技术有限责任公司 使用聚合物大孔吸附剂色谱分离有机酸
US9796948B2 (en) 2016-01-13 2017-10-24 The Procter & Gamble Company Laundry detergent compositions comprising renewable components
CN108341741A (zh) * 2017-01-23 2018-07-31 中国石油化工股份有限公司 一种合成气制备乙二醇的提纯精制工艺及装置
CN107583308B (zh) * 2017-10-19 2023-10-10 苏州苏震生物工程有限公司 一种用于1,3-丙二醇和2,3-丁二醇纯化的设备及工艺
CN110665256B (zh) * 2019-10-08 2021-01-08 中国科学院过程工程研究所 一种模拟移动床装置及分离多组分二元醇的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6291725B1 (en) * 2000-03-03 2001-09-18 Board Of Trustees Operating Michigan State University Catalysts and process for hydrogenolysis of sugar alcohols to polyols
US20020133049A1 (en) * 2000-03-29 2002-09-19 Archer-Daniels-Midland Company Method of recovering 1,3-propanediol from fermentation broth
US20050045560A1 (en) * 2003-08-29 2005-03-03 Boyd Brendan William Dewatering process

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2985589A (en) 1957-05-22 1961-05-23 Universal Oil Prod Co Continuous sorption process employing fixed bed of sorbent and moving inlets and outlets
US3040777A (en) 1959-04-10 1962-06-26 Universal Oil Prod Co Rotary valve
US3422848A (en) 1966-06-09 1969-01-21 Universal Oil Prod Co Multiport rotary disc valve with liner protection means
US3709812A (en) * 1970-10-16 1973-01-09 Gen Electric Carbon dioxide sensor
US3706812A (en) 1970-12-07 1972-12-19 Universal Oil Prod Co Fluid-solid contacting apparatus
US4476331A (en) 1982-02-11 1984-10-09 Ethyl Corporation Two stage hydrogenolysis of carbohydrate to glycols using sulfide modified ruthenium catalyst in second stage
US4402832A (en) 1982-08-12 1983-09-06 Uop Inc. High efficiency continuous separation process
US4478721A (en) 1982-08-12 1984-10-23 Uop Inc. High efficiency continuous separation process
US4642394A (en) 1985-07-16 1987-02-10 Celanese Corporation Production of propanediols
US4642397A (en) 1985-10-01 1987-02-10 Uop Inc. Process for separating isomers of dinitrotoluene
DE3928285A1 (de) 1989-08-26 1991-02-28 Basf Ag Verfahren zur herstellung niederer, mehrwertiger alkohole
US4966658A (en) * 1989-12-27 1990-10-30 Lloyd Berg Recovery of ethylene glycol from butanediol isomers by azeotropic distillation
US4935102A (en) 1989-12-27 1990-06-19 Lloyd Berg Separation of 2,3-butanediol from propylene glycol by azeotropic distillation
DE4106171A1 (de) 1991-02-27 1992-09-03 Siemens Ag Kassette und kassettenblock fuer lichtwellenleiter
IT1249956B (it) 1991-07-10 1995-03-30 Menon S R L Procedimento di idrogenazione catalitica della glicerina
IT1249955B (it) 1991-07-10 1995-03-30 Menon S R L Procedimento di idrogenazione della glicerina
US5432955A (en) 1994-05-23 1995-07-18 Plotka; Artur P. Quick release reusable sweatband
US5423955A (en) 1994-07-05 1995-06-13 Lloyd Berg Separation of propylene glycol from 1,2-butanediol by azeotropic
DE4442124A1 (de) 1994-11-26 1996-05-30 Basf Ag Verfahren zur Herstellung von Propandiol-1,2
US20020056686A1 (en) * 1996-06-14 2002-05-16 Agathagelos Kyrlidis Chromatography and other adsorptions using modified carbon adsorbents
FI20020592A (fi) * 2002-03-27 2003-09-28 Danisco Sweeteners Oy Menetelmä sokereiden, sokerialkoholien, hiilihydraattien ja niiden seosten erottamiseksi niitä sisältävistä liuoksista
CN101277920B (zh) * 2005-10-26 2013-06-19 三井化学株式会社 乙醇酸的制备方法
EP2038243A1 (fr) * 2006-10-27 2009-03-25 Archer-Daniels-Midland Company Procédés d'isolement ou de purification de propylène glycol et d'éthylène glycol, et produits dérivés de ces derniers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6291725B1 (en) * 2000-03-03 2001-09-18 Board Of Trustees Operating Michigan State University Catalysts and process for hydrogenolysis of sugar alcohols to polyols
US20020133049A1 (en) * 2000-03-29 2002-09-19 Archer-Daniels-Midland Company Method of recovering 1,3-propanediol from fermentation broth
US20050045560A1 (en) * 2003-08-29 2005-03-03 Boyd Brendan William Dewatering process

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GUENZEL B ET AL: "Adsorption von Diolen aus Fermentationsmedien an hydrophobe Zeolithe", CHEMIE INGENIEUR TECHNIK, WILEY VCH. VERLAG, WEINHEIM, DE, vol. 62, no. 9, 1 September 1990 (1990-09-01), pages 748 - 750, XP002158973, ISSN: 0009-286X *
VALORAN P. HANKO ET AL: "Determination of Carbohydrates, Sugar Alcohols, and Glycols in Cell Cultures and Fermentation Broths Using High-Performance Anion-Exchange Chromatography with Pulsed Amperometric Detection", ANALYTICAL BIOCHEMISTRY, vol. 283, no. 2, 2000, pages 192 - 199, XP002519275 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105985220A (zh) * 2014-11-26 2016-10-05 义守大学 醇类化合物的纯化方法

Also Published As

Publication number Publication date
US8177980B2 (en) 2012-05-15
US20090120878A1 (en) 2009-05-14

Similar Documents

Publication Publication Date Title
US8177980B2 (en) Separation of a mixture of polyhydric alcohols
CA1190482A (fr) Methode de separation des paraffines normales
US4851573A (en) Separation of citric acid from fermentation broth with a weakly basic anionic exchange resin adsorbent
JP6255406B2 (ja) 生体由来グリコール生成物からの有機塩の除去
US7514588B2 (en) Purification of organic solvents
US4882065A (en) Purification of sterols with activated carbon as adsorbent and chlorobenzene as desorbent
US4851574A (en) Separation of citric acid from fermentation broth with a strongly basic anionic exchange resin adsorbent
US4373025A (en) Process for the isomerization of glucose
JP2020523999A (ja) クロマトグラフィーを利用してd−プシコースボレート錯体からd−プシコースを生産する方法、及びd−プシコースを含む組成物
CN113548949B (zh) 一种1,1,3-三氯丙酮的生产方法
AU2015243402B2 (en) Process for the isolation of 1,2,5,6-hexanetetrol from sorbitol hydrogenolysis reaction mixtures using simulated moving bed chromotography
US20140155658A1 (en) Method for desorbing and regenerating butanol-adsorbing hydrophobic macroporous polymer adsorbent
US4588847A (en) Process for separation of ethylene glycol and propylene glycol on selected zeolites
US5177300A (en) Process for separating naphthalene from substituted benzene hydrocarbons
US10017439B2 (en) Process for the isolation of reaction products from sugar alcohol or anhydrosugar alcohol hydrogenolysis reaction mixtures using simulated moving bed chromatography
JP2650862B2 (ja) 芳香族炭化水素からメタキシレンの吸着分離法
JPS63287500A (ja) アラビノ−スの分離方法
Ray Adsorptive and membrane-type separations: A bibliographical update (1997)
KR20060077996A (ko) 생물학적 혼합물로부터 1,3-프로판디올 또는 글리세롤또는 그의 혼합물의 분리방법
EP0092193A2 (fr) Méthode pour isolement des tétracyclines
IE61021B1 (en) Separation of citric acid from fermentation broth
NZ205543A (en) Separating fatty acids using molecular sieves
CS211585B1 (en) Method of chromatographic separation of alditoles

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08849077

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08849077

Country of ref document: EP

Kind code of ref document: A1